JPH03296514A - Preparation of polyester (meth)acrylate - Google Patents
Preparation of polyester (meth)acrylateInfo
- Publication number
- JPH03296514A JPH03296514A JP9750090A JP9750090A JPH03296514A JP H03296514 A JPH03296514 A JP H03296514A JP 9750090 A JP9750090 A JP 9750090A JP 9750090 A JP9750090 A JP 9750090A JP H03296514 A JPH03296514 A JP H03296514A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acid
- acrylate
- polyester
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 19
- 239000000194 fatty acid Substances 0.000 claims abstract description 19
- 229930195729 fatty acid Natural products 0.000 claims abstract description 19
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 10
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 25
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 abstract description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 abstract description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 abstract description 6
- 239000005642 Oleic acid Substances 0.000 abstract description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 abstract description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000005886 esterification reaction Methods 0.000 abstract description 4
- 230000032050 esterification Effects 0.000 abstract description 3
- -1 oleic acid) Natural products 0.000 abstract description 3
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- JCLFHZLOKITRCE-UHFFFAOYSA-N 4-pentoxyphenol Chemical compound CCCCCOC1=CC=C(O)C=C1 JCLFHZLOKITRCE-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000000976 ink Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- YLAXZGYLWOGCBF-UHFFFAOYSA-N 2-dodecylbutanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)CC(O)=O YLAXZGYLWOGCBF-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（イ）発明の目的
〔産業上の利用分野〕
本発明は紫外線又は電子線の照射により、或はラジカル
重合触媒の存在下に常温において又は加熱等の硬化手段
によって硬化可能な硬化性化合物の製造方法に関するも
のであって、塗料又は平版印刷インキ等の各種の産業分
野において利用できるものである。Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention provides a method for curing by irradiation with ultraviolet rays or electron beams, or by curing means such as heating or the like in the presence of a radical polymerization catalyst at room temperature. The present invention relates to a method for producing curable compounds that can be used in various industrial fields such as paints or lithographic printing inks.
なお、本明細書においては、アクリレートとメタクリレ
ートを（メタ）アクリレートと、アクリロイル基とメタ
クリロイル基を（メタ）アクリロイル基と、またアクリ
ル酸とメタクリル酸を（メタ）アクリル酸と表わす。In this specification, acrylate and methacrylate are referred to as (meth)acrylate, acryloyl group and methacryloyl group are referred to as (meth)acryloyl group, and acrylic acid and methacrylic acid are referred to as (meth)acrylic acid.
（メタ）アクリレート系の活性エネルギー線硬化型化合
物を塗料又は平版印刷インキ等のビヒクルとして使用す
る場合、種々の特性が要求される２ＸＡ＋Ｃ＋Ｄ
が、特に親油性即ち天然油脂等に対する溶解性があるこ
とが要求され、その場合、硬化性と親油性のバランスが
問題となることが多い。すなわち、硬化性を改良するた
めには、化合物における１分子当たりの（メタ）アクリ
ロイル基含有量を増加させることが有効であるが、その
際エステル結合金有量も増加するため、化合物の極性が
増加し、親油性が低下する。When (meth)acrylate-based active energy ray-curable compounds are used as vehicles for paints or lithographic printing inks, 2XA+C+D, which requires various properties, is particularly lipophilic, that is, soluble in natural oils and fats. In such cases, the balance between curability and lipophilicity is often an issue. In other words, in order to improve the curability, it is effective to increase the content of (meth)acryloyl groups per molecule in the compound, but in this case, the amount of ester bonded gold also increases, so the polarity of the compound increases. increases and lipophilicity decreases.
硬化性を低下させずに高い親油性を得ることを目的とし
て、従来から種々の技１ネテが提案されている。例えば
、特公昭５Ｂ−５９４９号公報に記載された発明におい
ては、末端水酸基を有する、多価アルコールの（メタ）
アクリル酸エステルと多価インシアネートとの反応によ
って得られるウレタン（メタ）アクリレートを主成分と
し、ひまし油又はひまし油脂肪酸アルキルエステルを副
成分として含有させ、又特公昭５４−２２１２８号公報
に記載された発明においては、エポキシ樹脂と（メタ）
アクリル酸との反応によって得られるエポキシアクリレ
ートにおいて、エポキシ樹脂として、乾性油である大豆
油又はアマニ油等のエポキシ化物を用いている。Various techniques have been proposed in the past for the purpose of obtaining high lipophilicity without reducing curability. For example, in the invention described in Japanese Patent Publication No. 5B-5949, a polyhydric alcohol having a terminal hydroxyl group (meth)
The invention contains urethane (meth)acrylate obtained by the reaction of acrylic acid ester and polyvalent incyanate as the main component, contains castor oil or castor oil fatty acid alkyl ester as a subcomponent, and is also described in Japanese Patent Publication No. 54-22128. In, epoxy resin and (meth)
In the epoxy acrylate obtained by reaction with acrylic acid, an epoxidized product of drying oil such as soybean oil or linseed oil is used as the epoxy resin.
しかし、ウレタン（メタ）アクリレートは高価なもので
あり、エポキシ（メタ）アクリレートには、エステル化
の際に生成する２級の水酸基が残存するため、例えばこ
れを塗料化する等、親油性液体との混合の際に、乳化す
るという問題がある。However, urethane (meth)acrylate is expensive, and epoxy (meth)acrylate has residual secondary hydroxyl groups generated during esterification, so it can be used as a lipophilic liquid, such as in paints. There is a problem of emulsification during mixing.
又、エポキシ（メタ）アクリレートやウレタン（メタ）
アクリレートは、一般に極めて高粘度であり、単味で塗
料或いは平版印刷インキ等として取扱うには困難である
という問題がある。Also, epoxy (meth)acrylate and urethane (meth)
Acrylates generally have extremely high viscosity, and there is a problem in that it is difficult to handle them alone as paints, lithographic printing inks, or the like.
上記２種類の（メタ）アクリル酸エステル系化合物に比
較して安価で低粘度な化合物として、残存水酸基を有す
る、脂肪酸変性されたアルキッド型樹脂と（メタ）アク
リル酸とのエステル化により得られるポリエステルポリ
（メタ）アクリレートがある（特公昭５２−２３２３
）。A polyester obtained by esterifying a fatty acid-modified alkyd resin and (meth)acrylic acid, which has residual hydroxyl groups, is a cheaper and lower viscosity compound than the above two types of (meth)acrylic acid ester compounds. There is poly(meth)acrylate (Special Publication No. 52-2323
).
しかし、上記ポリエステルポリ（メタ）アクリレートに
おいて充分な親油性を得るためには、付加させる脂肪酸
の分子量を大きなものにするか、その付加当量を増加す
る必要がある。脂肪酸の分子量を増加した場合、脂肪酸
自身の融点が高くなるため、得られる樹脂が固形化し、
樹脂の取り扱いが非常に困難なものとなる。また、アル
キッド型樹脂を変成する際、脂肪酸の付加量を増加する
と、残存水酸基が減少するため、ポリエステルポリ（メ
タ）アクリレートにおける（メタ）アクリロイル基の導
入量が低下し、硬化性が著しく悪化する。従って、充分
な親油性を存し、かつ良好な硬化性を有する低粘度な液
状の活性工味ルギー線硬化型化合物を得ることは非常に
困難であった。However, in order to obtain sufficient lipophilicity in the polyester poly(meth)acrylate, it is necessary to increase the molecular weight of the fatty acid to be added or to increase its addition equivalent. When the molecular weight of the fatty acid is increased, the melting point of the fatty acid itself becomes higher, so the resulting resin solidifies.
The resin becomes very difficult to handle. Additionally, when modifying alkyd resins, increasing the amount of fatty acids added will reduce the amount of residual hydroxyl groups, resulting in a decrease in the amount of (meth)acryloyl groups introduced into polyester poly(meth)acrylate, resulting in a marked deterioration of curability. . Therefore, it has been extremely difficult to obtain a low-viscosity, liquid activated Lugie wire-curable compound that has sufficient lipophilicity and good curability.
本発明は上記問題点を解決し、速硬化性を有しかつ親油
性に優れた低粘度なポリエステルポリ（メタ）アクリレ
ートの製造方法を提供することを課題とする。An object of the present invention is to solve the above-mentioned problems and provide a method for producing a low-viscosity polyester poly(meth)acrylate that has fast curing properties and excellent lipophilicity.
（１１）発明の構成
〔課題を解決するための手段〕
本発明者等は、速硬化性と高い親油性の相反する特性を
両立できる化合物の製造方法を提供すべく鋭意検討した
結果、全炭素数が９以上である分枝状の脂肪族飽和二塩
基酸及び／又は該二塩基酸無水物を原料の１成分として
用いて、１分子中に３個以上の１級水酸基を有する多価
アルコール、炭素数１０〜２０の脂肪酸及び（メタ）ア
クリル酸と特定範囲の割合で反応させることにより、速
硬化性を有しかつ親油性の優れた低粘度なポリエステル
ポリ（メタ）アクリレートを得ることができることを見
出し、本発明を完成するに至った。(11) Structure of the Invention [Means for Solving the Problems] As a result of intensive studies to provide a method for producing a compound that can achieve both the contradictory properties of fast curing and high lipophilicity, the present inventors discovered that A polyhydric alcohol having three or more primary hydroxyl groups in one molecule, using a branched aliphatic saturated dibasic acid having a number of 9 or more and/or the dibasic acid anhydride as one component of the raw material. By reacting with a fatty acid having 10 to 20 carbon atoms and (meth)acrylic acid in a specific range of ratios, it is possible to obtain a low-viscosity polyester poly(meth)acrylate that has fast curing properties and excellent lipophilicity. We have discovered that this can be done, and have completed the present invention.
即ち、本発明は、
（ａ）全炭素数が９以上である分枝状の脂肪族飽和二塩
基酸及び／又は該二塩基酸無水物Ａモル、（ｂ）分子中
にＮ個の１級水酸基を有する多価アルコール８モル、
（ｃ）炭素数１０〜２０の脂肪酸Ｃモル及び（ｄ）アク
リル酸及び／又はメタクリル酸０モルをエステル化する
ポリエステルポリアクリレート及び／又はポリエステル
ポリメタクリレートの製造方法である。That is, the present invention provides: (a) A mole of a branched aliphatic saturated dibasic acid and/or the dibasic acid anhydride having a total carbon number of 9 or more; (b) N primary primary acids in the molecule; A method for producing polyester polyacrylate and/or polyester polymethacrylate by esterifying 8 mol of polyhydric alcohol having a hydroxyl group, (c) C mol of fatty acid having 10 to 20 carbon atoms, and (d) 0 mol of acrylic acid and/or methacrylic acid. It is.
ただし、上記Ａ、Ｂ、Ｃ及びＤは、それぞれ下記の条件
を同時に満たす数値である。However, the above A, B, C, and D are numerical values that simultaneously satisfy the following conditions.
（１）３≦Ｎ
（３）２≦□≦５
以下、本発明に用いる成分及び製造方法について詳述す
る。(1) 3≦N (3) 2≦□≦5 The components and manufacturing method used in the present invention will be described in detail below.
（成分）
Ｏ脂肪族飽和二塩基酸又は該二塩基酸無水物本発明にお
いて使用する脂肪族飽和二塩基酸又は該二塩基酸無水物
〔以下（ａ）成分という］は、全炭素数が９以上であり
且つ分枝状である。全炭素数が９より少ないと、得られ
るポリエステルポリ（メタ）アクリレートの親油性が低
く、又分枝状でないと硬化性が低いという問題がある。(Component) O Aliphatic saturated dibasic acid or dibasic acid anhydride The aliphatic saturated dibasic acid or dibasic acid anhydride used in the present invention [hereinafter referred to as component (a)] has a total carbon number of 9 It is above and branched. If the total number of carbon atoms is less than 9, the resulting polyester poly(meth)acrylate will have low lipophilicity, and if it is not branched, it will have low curability.
（ａ）成分の全炭素数は、９以上であれば特に制限はな
いが、比較的低粘度であり取扱が容品なポリエステルポ
リ（メタ）アクリレートを得るためには、２０以下であ
ることが好ましい、脂肪族飽和二塩基酸又は咳二塩基酸
無水物の好ましい例としては、メチルへキサヒドロフタ
ル酸、ＹＨ−３０６（油化シェルエポキシ■製；側鎖炭
素数１０の二塩基酸）、ドデシルコハク酸及びその無水
物等がある。The total carbon number of component (a) is not particularly limited as long as it is 9 or more, but it should be 20 or less in order to obtain a polyester poly(meth)acrylate that has a relatively low viscosity and is easy to handle. Preferred examples of aliphatic saturated dibasic acids or dibasic acid anhydrides include methylhexahydrophthalic acid, YH-306 (manufactured by Yuka Shell Epoxy ■; dibasic acid having 10 side chain carbon atoms), Examples include dodecylsuccinic acid and its anhydride.
○多価アルコール
本発明において使用する多価アルコール〔以下（ｂ）成
分という〕は、１級炭素に結合した水酸基、即ち１級水
酸基を１分子中に３個以上有する多価アルコールであり
、好ましい具体例としては、トリメチロールプロパン、
ペンタニルスリトール及びジペンタエルスリトール等が
ある。○Polyhydric alcohol The polyhydric alcohol used in the present invention [hereinafter referred to as component (b)] is a polyhydric alcohol having three or more hydroxyl groups bonded to a primary carbon, that is, three or more primary hydroxyl groups in one molecule, and is preferable. Specific examples include trimethylolpropane,
Examples include pentanylthritol and dipentaerthritol.
もし、２級炭素に結合した水酸基、即ち２級水酸基を分
子中に有する多価アルコールを使用すると、２級水酸基
とカルボキシル基とのエステル化反応が進行しないため
、生成物には遊離の水酸基が残存する結果、生成物は親
油性液体との混合の際に乳化してしまうという問題があ
る。If you use a polyhydric alcohol that has a hydroxyl group bonded to a secondary carbon, that is, a secondary hydroxyl group in its molecule, the esterification reaction between the secondary hydroxyl group and the carboxyl group will not proceed, so the product will contain free hydroxyl groups. As a result of remaining, there is a problem that the product emulsifies when mixed with lipophilic liquids.
Ｏ脂肪酸
本発明において使用する脂肪酸（以下（ｃ）成分という
〕は、炭素数１０〜２０の飽和及び不飽和脂肪酸であり
、好ましい具体例としては、例えばカプリン酸、ラウリ
ン酸、ミリスチン酸、バルミチン酸、ステアリン酸、オ
レイン酸、ヤシ油脂肪酸、ヌカ油脂肪酸、アマニ油脂肪
酸、桐油脂肪酸及びヒマシ油脂肪酸等がある。O fatty acids The fatty acids used in the present invention (hereinafter referred to as component (c)) are saturated and unsaturated fatty acids having 10 to 20 carbon atoms, and preferred specific examples include capric acid, lauric acid, myristic acid, and valmitic acid. , stearic acid, oleic acid, coconut oil fatty acid, bran oil fatty acid, linseed oil fatty acid, tung oil fatty acid, and castor oil fatty acid.
○（メタ）アクリル酸
本発明において使用する（メタ）アクリル酸〔以下（ｄ
）成分という］は、工業的に広く一般に使用されている
ものでよい。○ (meth)acrylic acid (meth)acrylic acid used in the present invention [hereinafter (d
) component] may be one that is widely and generally used industrially.
（各成分の反応割合）
本発明において親油性と硬化性を併せ持つポリエステル
ポリ（メタ）アクリレートを得るためには、各成分を次
の範囲内で反応させなければならない。(Reaction ratio of each component) In order to obtain a polyester poly(meth)acrylate having both lipophilicity and curability in the present invention, each component must be reacted within the following range.
即ち、Ａモルの（ａ）成分、Ｂモルの（ｂ）成分、Ｃモ
ルの（ｃ）成分及びＤモルの（ｄ）成分を反応させる場
合において、上記Ａ、Ｂ、Ｃ及びＤは、それぞれ下記の
条件を同時に満たす数値でなければならない。That is, when reacting A mole of component (a), B mole of component (b), C mole of component (c), and D mole of component (d), the above A, B, C, and D are each The value must satisfy the following conditions at the same time.
（１）３≦Ｎ
２ＸＡ＋Ｃ十〇
（３）２≦ □ ≦５
ＮＸＢ／ （２ＸＡ＋Ｃ＋Ｄ）で表される比は、エステ
ル結合を形成する水酸基とカルボキシル基との比を示す
ものであり、この比が０．９より小さいか、１．１より
大きいと、生成物に未反応の水酸基或はカルボキシル基
が残存するため、ポリエステルポリ（メタ）アクリレー
トの耐乳化性、即ち親油性液体との混和性が低下すると
いう問題がある。脂肪酸と（メタ）アクリル酸のモル比
Ｄ／Ｃの値が５より大きい場合、脂肪酸の付加モル数が
少なくなりすぎて、ポリエステルポリ（メタ）アクリレ
ートの親油性が低下し、Ｄ／Ｃが２より小さい場合、ポ
リエステルポリ（メタ）アクリレート中の（メタ）アク
リロイル基の含有量が少なくなりすぎるため、ポリエス
テルポリ（メタ）アクリレートの硬化性が低下するとい
う問題がある。(1) 3 ≦ N 2 If it is smaller than 0.9 or larger than 1.1, unreacted hydroxyl groups or carboxyl groups remain in the product, which impairs the emulsification resistance of the polyester poly(meth)acrylate, that is, the miscibility with lipophilic liquids. There is a problem with the decline. When the value of the molar ratio D/C of fatty acid and (meth)acrylic acid is larger than 5, the number of added moles of fatty acid becomes too small, the lipophilicity of the polyester poly(meth)acrylate decreases, and D/C becomes 2. If it is smaller, the content of (meth)acryloyl groups in the polyester poly(meth)acrylate becomes too small, resulting in a problem that the curability of the polyester poly(meth)acrylate decreases.
（製造方法）
本発明の製法は次のようにして行うことが出来る。即ち
、好ましくは撹拌機、温度計及び水分離器を備えた反応
機に、（ａ）成分、（ｂ）成分、（ｃ）成分及び（ｄ）
成分を、順不同で所定量仕込み、加熱する。このとき、
脱水共沸剤を兼ねた反応溶媒、エステル化触媒及び重合
防止剤も同時に仕込むことが好ましい。(Manufacturing method) The manufacturing method of the present invention can be carried out as follows. That is, component (a), component (b), component (c) and component (d) are placed in a reactor preferably equipped with a stirrer, a thermometer and a water separator.
Predetermined amounts of ingredients are added in random order and heated. At this time,
It is preferable that a reaction solvent that also serves as a dehydration entrainer, an esterification catalyst, and a polymerization inhibitor are added at the same time.
反応中に生成する水は、反応溶媒との共沸混合物として
系外に除去され、反応の終点は副生ずる水の量で決定す
ればよい。Water produced during the reaction is removed from the system as an azeotrope with the reaction solvent, and the end point of the reaction may be determined by the amount of water produced as a by-product.
反応終了後、反応液を水洗し、水層を分離除去後、減圧
下で有機層中の溶媒を留去することにより、目的化合物
であるポリエステルポリ（メタ）アクリレートを得る。After the reaction is completed, the reaction solution is washed with water, the aqueous layer is separated and removed, and the solvent in the organic layer is distilled off under reduced pressure to obtain the target compound, polyester poly(meth)acrylate.
以上の様にして得られるポリエステルポリ（メタ）アク
リレートを硬化させるには、紫外線又は電子線等の活性
エネルギー線を照射させたり、ラジカル重合触媒の存在
下に常温で放置するか加熱すればよく、紫外線の照射に
より硬化させる場合には光増感剤を、常温で又は加熱に
より硬化させる場合には過酸化物等の熱分解型開始剤を
含有させることが好ましい。In order to cure the polyester poly(meth)acrylate obtained as described above, it may be irradiated with active energy rays such as ultraviolet rays or electron beams, left at room temperature in the presence of a radical polymerization catalyst, or heated. It is preferable to contain a photosensitizer when curing by irradiation with ultraviolet rays, and a thermal decomposition type initiator such as peroxide when curing at room temperature or by heating.
本発明によって得られるポリエステルポリ（メタ）アク
リレートは、速硬化性及び親油性を兼ね備えており、さ
らに低粘度であるので、これらの特性が要求される種々
の用途に利用でき、特に塗料又は平版印刷インキ等のビ
ヒクルとして有用である。The polyester poly(meth)acrylate obtained by the present invention has both fast curing properties and lipophilic properties, and also has a low viscosity, so it can be used in various applications that require these properties, especially in coatings and lithographic printing. It is useful as a vehicle for ink, etc.
本発明によって得られるポリエステルポリ（メタ）アク
リレートを、塗料又は平版印刷インキ等のビヒクルとし
て利用するには、顔料、増感剤、安定剤及びワックス等
、通常使用される添加剤を含有させればよい。In order to utilize the polyester poly(meth)acrylate obtained by the present invention as a vehicle for paints or lithographic printing inks, it is necessary to contain commonly used additives such as pigments, sensitizers, stabilizers, and waxes. good.
次に実施例及び比較例を挙げて、本発明をさらに具体的
に説明する。Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例１
撹拌機、温度計及び水分離器を備えた反応機に、ドデシ
ルコハク酸無水物（全炭素数が１２である分枝状脂肪族
飽和二塩基酸無水物）２９９ｇ（１゜１５モル）、ペン
タエリスリトール３１２．８ｇ（２，３モル）、オレイ
ン酸３２３．７ｇ（１，１５モル）、アクリル酸４１４
．０ ｇ （５，７５モル）、ｐ−トルエンスルホン酸
２６ｇ、フェノチアジンｌ。Example 1 299 g (1°15 mol) of dodecylsuccinic anhydride (branched aliphatic saturated dibasic acid anhydride having a total carbon number of 12) was placed in a reactor equipped with a stirrer, a thermometer, and a water separator. ), pentaerythritol 312.8g (2.3 mol), oleic acid 323.7g (1.15 mol), acrylic acid 414
．． 0 g (5,75 mol), 26 g p-toluenesulfonic acid, l phenothiazine.
Ｏｇ、トルエン１３５０ｇを仕込み、撹拌しつつ加熱し
た。内温が１０５°Ｃになると、反応により生成した水
がトルエンとの共沸混合物として流出し始めた。水分離
器により水は系外に抜き取った。1,350 g of toluene were charged and heated while stirring. When the internal temperature reached 105°C, water produced by the reaction began to flow out as an azeotrope with toluene. Water was removed from the system using a water separator.
反応開始後６時間で反応は纒了し、水は１４０゜２ｍｌ
留出していた。反応終了後反応液を水洗し水層を分離後
、減圧下で溶媒を留去して目的とするポリエステルポリ
（メタ）アクリレート１１２５ｇを得た。この生成物
を化合物ｌとする。The reaction was completed 6 hours after the start of the reaction, and the amount of water was 140°2ml.
He was a distiller. After the reaction was completed, the reaction solution was washed with water, the aqueous layer was separated, and the solvent was distilled off under reduced pressure to obtain 1125 g of the desired polyester poly(meth)acrylate. This product is designated as compound 1.
実施例２
二塩基酸としてＹＨ−３０６（全炭素数が１６である分
枝状脂肪族飽和二塩基酸）を２６９．５ ｇ（１，１５
モル）用いる以外は実施例１と全く同様に反応を行い、
ポリエステルポリ（メタ）アクリレート１０７０ｇを得
た。この生成物を化合物２とする。Example 2 269.5 g (1,15
The reaction was carried out in exactly the same manner as in Example 1 except that mol) was used,
1070 g of polyester poly(meth)acrylate was obtained. This product is designated as compound 2.
実施例３
オレイン酸６４７．４ｇ（２，３モル）、アクリル酸３
３１．２ｇ（４，６モル）を用いる以外は実施例１と全
く同様に反応を行い、ポリエステルポリ（メタ）アクリ
レート１２３０ｇを得た。この生成物を化合物３とする
。Example 3 647.4 g (2.3 moles) of oleic acid, 3 acrylic acid
The reaction was carried out in exactly the same manner as in Example 1 except that 31.2 g (4.6 mol) was used, and 1230 g of polyester poly(meth)acrylate was obtained. This product is designated as compound 3.
比較例１
分岐を有していない芳香族二塩基酸であるフタル酸を１
７０．２ｇ（１，１５モル）用いる以外は実施例１と全
く同様に反応を行い、ポリエステルポリ（メタ）アクリ
レート１０７０ｇを得た。この生成物を化合物４とする
。Comparative Example 1 Phthalic acid, which is a non-branched aromatic dibasic acid, was
The reaction was carried out in exactly the same manner as in Example 1, except that 70.2 g (1.15 mol) was used, and 1070 g of polyester poly(meth)acrylate was obtained. This product is designated as compound 4.
比較例２
オレイン酸９７１．１ｇ（３，４５モル）、アクリル酸
２４８．４ ｇ （３，４５モル）を用いる以外は実施
例１と全（同様に反応を行い（オレイン酸に対するアク
リル酸のモル比は１）、ポリエステルポリ （メタ）ア
クリレ−）１３８０ｇを得た。この生成物を化合物５と
する。Comparative Example 2 The reaction was carried out in the same manner as in Example 1 except that 971.1 g (3.45 mol) of oleic acid and 248.4 g (3.45 mol) of acrylic acid were used (mol of acrylic acid relative to oleic acid). The ratio was 1), and 1,380 g of polyester (poly(meth)acrylate) was obtained. This product is designated as compound 5.
上記実施例１〜３及び比較例１〜２において得た化合物
１〜５を用いて、粘度、ケロシン熔解性及び硬化性を評
価し、下記表１に示す結果を得た。Viscosity, kerosene solubility, and curability were evaluated using Compounds 1 to 5 obtained in Examples 1 to 3 and Comparative Examples 1 to 2, and the results shown in Table 1 below were obtained.
表１ なお、各種特性の評価は以下の方法により行った。Table 1 In addition, evaluation of various characteristics was performed by the following method.
〈粘度〉
化合物１〜５の粘度（２５°Ｃ）をＥ型粘度計（■東京
理科工業所製ＶＩＳＣＯＮＩＣＥＭＤ型〕を用いて測定
した（単位はＣρＳである）。<Viscosity> The viscosity (25° C.) of Compounds 1 to 5 was measured using an E-type viscometer (VISCO NICEMD type manufactured by Tokyo Rika Kogyo Co., Ltd.) (unit: CρS).
〈ケロシン溶解性〉
化合物１〜５の１０．０ ｇにケロシンを溶液が白濁す
るまで添加し、白濁点までに添加されたケロシンの量を
測定した。なお、ケロシンの添加量が多い程１．望の親
油性が大きいことを示す。<Kerosine Solubility> Kerosene was added to 10.0 g of Compounds 1 to 5 until the solution became cloudy, and the amount of kerosene added up to the cloudy point was measured. Note that the greater the amount of kerosene added, the more 1. This shows that the desired lipophilicity is large.
〈硬化性〉
化合物１〜５に５＠ｔＸの光開始剤〔日本チバガイギー
■製商品名イルガキュアー６５１〕を添加したものを基
板上に５μの厚みで塗布したサンプルを、コンベアーに
乗せて、８０ｋＷ／ｃｍ集光型高圧水銀灯（焦点距離１
０ｃｓ＋）の下を通過させることによりサンプル上の塗
膜を硬化させ、塗膜表面のタンクをなくすことができた
コンベアースピードの最大値（単位はｍ／ｍｉｎ、であ
る）をもって硬化性とした。<Curability> A sample prepared by adding 5@tX photoinitiator [trade name Irgacure 651 manufactured by Nippon Ciba Geigy] to compounds 1 to 5 and coating it on a substrate with a thickness of 5μ was placed on a conveyor and heated at 80kW. /cm condensing high pressure mercury lamp (focal length 1
The coating film on the sample was cured by passing it under 0cs+), and the maximum conveyor speed (unit: m/min) that could eliminate the tank on the surface of the coating film was defined as curability.
（ハ）〔発明の効果〕
本発明により得られるポリエステルポリ（メタ）アクリ
レートは、高い親油性、速硬化性及び低粘度を併せ持つ
化合物であり、例えば塗料又は平版印刷用インキとして
特に有用なものである。(C) [Effects of the Invention] The polyester poly(meth)acrylate obtained by the present invention is a compound that has high lipophilicity, fast curing property, and low viscosity, and is particularly useful as, for example, a paint or a lithographic printing ink. be.
本発明により提供されるポリエステルポリ（メタ）アク
リレートを用いて、平版印刷用インキを製造することに
よって、種々の特性を満足し、特に硬化速度が速いこと
によって生産性を著しく向上させることができ、その工
業的価値は極めて大である。By producing a lithographic printing ink using the polyester poly(meth)acrylate provided by the present invention, it satisfies various properties, and in particular, productivity can be significantly improved due to the fast curing speed. Its industrial value is extremely large.
Claims (1)
二塩基酸及び／又は該二塩基酸無水物Ａモル、 （ｂ）分子中にＮ個の１級水酸基を有する多価アルコー
ルＢモル、 （ｃ）炭素数１０〜２０の脂肪酸Ｃモル及び（ｄ）アク
リル酸及び／又はメタクリル酸Ｄモルをエステル化する
ポリエステルポリアクリレート及び／又はポリエステル
ポリメタクリレートの製造方法。 ただし、上記Ａ、Ｂ、Ｃ及びＤは、それぞれ下記の条件
を同時に満たす数値である。 （１）３≦Ｎ （２）０．９≦（Ｎ×Ｂ）／（２×Ａ＋Ｃ＋Ｄ）≦１．
１（３）２≦Ｄ／Ｃ≦５[Claims] 1. (a) A mole of a branched aliphatic saturated dibasic acid and/or anhydride of the branched aliphatic acid having a total number of carbon atoms of 9 or more, (b) N in the molecule. B mol of polyhydric alcohol having a primary hydroxyl group, (c) C mol of fatty acid having 10 to 20 carbon atoms, and (d) D mol of acrylic acid and/or methacrylic acid of polyester polyacrylate and/or polyester polymethacrylate for esterifying. Production method. However, the above A, B, C, and D are numerical values that simultaneously satisfy the following conditions. (1) 3≦N (2) 0.9≦(N×B)/(2×A+C+D)≦1.
1 (3) 2≦D/C≦5
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9750090A JP2797628B2 (en) | 1990-04-16 | 1990-04-16 | Method for producing polyester poly (meth) acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9750090A JP2797628B2 (en) | 1990-04-16 | 1990-04-16 | Method for producing polyester poly (meth) acrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03296514A true JPH03296514A (en) | 1991-12-27 |
| JP2797628B2 JP2797628B2 (en) | 1998-09-17 |
Family
ID=14193986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9750090A Expired - Fee Related JP2797628B2 (en) | 1990-04-16 | 1990-04-16 | Method for producing polyester poly (meth) acrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2797628B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5418301A (en) * | 1992-02-26 | 1995-05-23 | Perstorp Ab | Dendritic macromolecule and process for preparation thereof |
| WO2011129390A1 (en) * | 2010-04-15 | 2011-10-20 | 太陽ホールディングス株式会社 | Processes for producing polyester and modification product thereof |
| WO2016006497A1 (en) * | 2014-07-07 | 2016-01-14 | 東亞合成株式会社 | Active-energy-ray-curable composition |
| JP2017538793A (en) * | 2014-09-26 | 2017-12-28 | ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー | Non-fluorinated monomers and non-fluorinated polymers for surface effect compositions |
-
1990
- 1990-04-16 JP JP9750090A patent/JP2797628B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5418301A (en) * | 1992-02-26 | 1995-05-23 | Perstorp Ab | Dendritic macromolecule and process for preparation thereof |
| WO2011129390A1 (en) * | 2010-04-15 | 2011-10-20 | 太陽ホールディングス株式会社 | Processes for producing polyester and modification product thereof |
| CN102844352A (en) * | 2010-04-15 | 2012-12-26 | 太阳控股株式会社 | Processes for producing polyester and modification product thereof |
| JPWO2011129390A1 (en) * | 2010-04-15 | 2013-07-18 | 太陽ホールディングス株式会社 | Method for producing polyester and modified product thereof |
| WO2016006497A1 (en) * | 2014-07-07 | 2016-01-14 | 東亞合成株式会社 | Active-energy-ray-curable composition |
| JP2017538793A (en) * | 2014-09-26 | 2017-12-28 | ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー | Non-fluorinated monomers and non-fluorinated polymers for surface effect compositions |
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| JP2797628B2 (en) | 1998-09-17 |
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